Composition of matter



Patented Nov. 10, 1942 COMPOSITION OF MATTER Lyle W. Rothenberger, Brunswick, 6a., assignor to Hercules Powder Company, Del., a corporation of Delaware Wilmington,

No Drawing. Application October 16, 1940, Serial No. 361,389

11 Claims.

This invention relates to a composition of matter containing a material which is normally subject to decomposition or deterioration upon ageing and an anti-oxidant for said material. More particularly, it relates to a composition containing rosin or a rosin derivative as an important or principal constituent and a small amount of an anti-oxidant therefor which comprises a condensation product of a terpene halo-alkyl ether such as terpinyl beta-chloroethyl ether with an amine such as aniline.

Various materials, such as rubber, gasoline, soaps, fatty oils, linoxyn, rosin and derivatives thereof such as for example ester gum, dry rosin size, etc. are subject to spontaneous decomposition or deterioration upon ageing while exposed to light, oxygen, heat, or combinations of such influences. Attempts have been made to prevent such action upon ageing by blending with such materials small amounts of anti-oxidants. However, so far as is known, non of these attempts has been entirely successful commercially because of high cost or ineffectiveness of the antioxidant, and for other reasons.

It is an object of this invention to provide an improved anti-oxidant.

Another object is to provide an improved antioxidant for use with rosin and rosin derivatives such as rosin soaps, rosin esters, and resin sizes such as dry rosin size.

A still further object is to provide an improved composition of matter containing a substantial proportion of an organic material normally subject to oxidation upon agein and an anti-oxidant therefor.

Still other objects will more fully hereinafter appear.

In accordance with the present invention, these objects are accomplished by admixing with the organic material which is subject to deterioration upon ageing a condensation product of an ether of a terpene radical and a halogen substituted organic radical with an amine.

As the organic material to be inhibited against oxidation, I have found that rosin, rosin derivatives such as ester gum, rosin soaps, rosin-containing soaps, dry rosin size, etc., and rubber and compositions containing such materials are particularly suitable. However, anti-oxidant characteristics may be found to be imparted by the anti-oxidants of the present invention to various other organic materials such as unsaturated fatty oils such as castor oil, linseed-oil, insulating and lubricating oils, petroleum oils, gasoline, unsaturated fatty oils, transformer oils, linoxyn, fatty oil-containing plastics, varnishes and coating compositions, fatty acids particularly the unsaturated fatty acids, fatty acid soaps, alkali rosinate-containing fatty acid soaps, etc. and plastic and liquid compositions containing the foregoing product.

materials. If desired, coating .compositions such as ester gum-containing varnishes may embody a suitable amount of the anti-oxidant of the present invention to yield a film of enhanced durability. Likewise, compositions made with free wood or gum rosin such as rosin-containing paints, varnishes, adhesives, soldering fluxes,

compositions containing powdered rosin or otherwise presenting a large surface of rosin to the air, etc. may have incorporated therein th anti-oxidant of the present invention. Similarly compositions containing powdered dry alkali rosinate such as dry rosin size. may be commingled with the anti-oxidant. It is well recognized that dry rosin sizes are particularly subject to rapid oxidation upon ageing frequently resulting in the starting of fires during handling or storage and causing deterioration in the quality of the size.

The anti-oxidant may be prepared in accordance with the method described in my copending application, Serial No. 353,529, filed August 21, 1940, of which this application is a continuationin-part.

In accordance with the method of said application, an ether of a terpene radical and a halogen substituted organic radical, such as terpinyl beta-chloroethyl ether, is condensed with an amine in the presence, if desired, of a relatively small amount of catalyst such as a hydrohalideamine addition product such as the hydrochloride addition product of the amine undergoing condensation.

Of the condensation products, the preparation of which is described in the above-identified application, the secondary and tertiary condensation products resulting from condensation with a primary and a secondary amine respectively are preferably employed, and of these that resulting from condensation with the primary aromatic amine aniline is preferred. Condensation with a primary amine yields a secondary amine Condensation with a secondary amine yields a tertiary amine condensation product. Condensation with a tertiary amine yields a quaternary amine condensation product.

Other terpene ethers which are suitable are, for example, terpinyl chloropropyl ether, terpinyl chlorobutyl ether, terpinyl chloroamyl ether, terpinyl chlorooctyl ether, terpinyl chlorophenyl ether, terpinyl ether of glycerine monochlorohydrin, terpinyl chlorooctadecamethylene ether, etc., the corresponding fenchyl, bornyl, isobornyl, etc. ethers, and the corresponding bromoand iodo-substituted ethers. The terpene radical may be either a hydrocarbon radical or an oxygenated hydrocarbon radical such as a terpene radical containing one or more oxygen-containing groups such as hydroxy groups, keto groups, carboxyl groups, etc. The organic group may contain one or more halogen groups. Thus, terpinyl dichloropropyl ether, prepared by reacting alpha pinene with glycerlne dichlorohydrin may be employed.

The condensation between the ether and the amine proceeds most readily when using an iodine substituted ether, less readily when using a bromine substituted ether and still less readily when using a chlorine substituted ether. However, in view of the difliculty and expense of preparing the iodine substituted ethers and the bromine substituted ethers, the chlorine substituted ethers are preferred. The halogen atom on the alkyl group may be primary, secondary,

or tertiary and the point of etherification of they alkyl group may likewise be at ondary, or tertiary position.

As examples of suitable amines for use in the condensation reaction, the following may be named: primary aromatic amines such as aniline, toluidine, alpha. naphthylamine, beta. naphthyiamine, etc.; secondary aromatic amines such as methyl aniline, diphenyl amine, etc.; aralkyl amines such as benzyl amine; aliphatic amines such as methyl, ethyl, propyl, butyl, and octyl amine, dimethyl, diethyl, dipropyl, dibutyl, diamyl and dioctyl amine, etc.; diamines such as ethylene diamine, phenylene diamine, etc.; mixed aliphaticamines such as methyl ethyl amine, ethyl butyl amine, etc. Where a polyamine is employed, one mol thereof is equivalent to a number of mols of a mono amine equal to the number of aminyl groups present in the polyamine. Thus, where a diamine is employed only one half of the usual molar quantity thereof need be used.

The condensation product prepared in accorda primary, secance with the foregoing may be characterized by the general formula where T is a terpene radical such as terpinyl, where R is an alkyl group, and where R1 and R2 are either hydrogen or an organic radical such as an aliphatic group, aromatic group, and aralkyl group, an alkaryl group, etc. Preferably, at least one of R1 and R2 is a hydrocarbon radical of the type just described.

While it is believed that the condensation involves principally the reaction of the halo alkyl terpene ether with the amine and the halogen center, under some circumstances where the terpene halo-alkyl ether contains unsaturated double bonds, reaction with the amine takes place additionally at such double bonds. The amount of condensation of the amine at unsaturated centers of the terpene ether may be greatly reduced by the use of molar proportions of the reactant or by carrying the reaction out in the absence of a catalyst. The product of such condensation may be characterized by the general formula where T, R, R1, and R2 have the same significance as above. For example, where terpinyl beta-chlorethyl ether is reacted with aniline under conditions which give rise to suchv condensation, the product is believed to be characterized by the following formula:

be an amine hydrohalide addition product in an amount ranging from about 0.2 to about 0.5 mol per mol of ether taken. Examples,- of catalysts other than amine hydrohalide addition products which may be used are hydroiodic acid, hydrobromic acid, hydrochloric acid, ferrous iodide, sulfuric acid, acetic acid, p-toluene sulfonic acid, etc. Following the reaction, the mixture is allowed to cool and then treated with an alkali so as to decompose hydrohalideeamine catalyst and hydrohalide-condensate addition products, and treated to recover the condensation product.

Preferably, the reactants are employed in such proportion that from about 1 to about 4 mols of the amine are present for each mol of the ether to be condensed. Where the amine is a polyamine, or where a poly halogen substituted terpene ether containing a plurality of halogen groups on a single organic radical or a plurality of halogen substituted ctherifled organic groups, the molar proportions are adjusted accordingly so that there is presented by the amine from about 1 to about 4 amine groups per halogen group in the etherifled organic radical or radicals of said ether.

Usually, the mixture is agitated during the reaction ether by the provision of a suitable agitator or as a result of the heating or refluxing of the mixture. If desired, the reaction may be carried out under elevated pressure in a suitable autoclave.

The use of equimolar proportions of the ether and the amine will yield the desired condensation product with somewhat less side reaction. However, the use of an excess of the amine is frequently desirable in order to effect better yield on the basis of the ether taken.

Although the use of a catalyst increases somewhat the amount of by-products produced, such use of the catalyst is generally desirable because of the more rapid condensation eflected thereately hydrohalide addition products or is a result or the incorporation in the reacting nixtine of a hy halide such as hydrochloric, iydrobromic, or hydroiodic acid which reacts with the mine.

The reaction temperature may vary between about 100 C. and about 250 0., but is preferably within the range of from about 170 C. to about 210 C. The reaction period may range from about 1 to about 24 hours. but is preferably between about 4 and about 10 hours.

As the ether employed in carrying out the condensation of the present invention, there may be used terpinyl beta-chloroethyl ether prepared the manner described in the co-pending application of D. H. Sheflield, Serial No. 301,761, filed October 28, 1939. A method described in that application for the production. of this ether is as followsz-400 g. of alpha pinene were added to 600 g. of ethylene chlorohydrin and 12 g. of 75% by weight sulfuric acid and the mixture well agitated. The reaction which took place evolved heat, the temperature being maintained at 45 C. by cooling. After. 3 hours, the reaction was complete. Acid and excess ethylene chlorohydrin were then removed by two washes of about 500 g. of 10% by weight aqueous sodium carbonate solution. The resulting oil was then fractionated into two components by distillation. The fraction coming over between 115 and 130 C. at 8 mm. absolute pressure consisted essentially or terpinyl beta-chloroethyl ether. This compound may be characterized by the followin formula:

CHI

Hi CH:

When the terpinyl beta-chloroethyl ether having the foregoing structural formula is condensed with aniline, the principal condensation product may be designated as terpinyl beta-monoethyl aniline ether (1. e. the mono-anilide of the ethyl ether of alpha terpineol) and may be characterized by the following formula:

HaC

alkali must be used per mol of terpene halo-alkyl ether employed in order to give complete neutralization. Following treatment with alkali, the product may be washed with water, dried or purified in any suitable manner, as by distillation to remove unreacted amine therefrom and to recover the pure product.

It is preferable to carry out the condensation in the absence of water. since the presence of water in substantial amounts in the reaction mixture reduces materially the yield of product and the speed of reaction. If desired, the reaction may be carried out under pressure which may vary from atmospheric up to atmospheres, so as to promote a rapid reaction.

In accordance with the present invention, the condensation product is into the organic material to be inhibited against oxidation in any desired manner, as by melting therewith, forming a solution of the anti-oxidant and the organic material in a mutual volatile organic solvent, dissolving the anti-oxidant in the organic material where it is in liquid form or capable of being rendered liquid, milling or grinding the anti-oxidant with the organic material as upon a roll mill, such as hot rolls, in a Banbury mixer, Werner Pfleiderer mixer. ball mill, hammer mill, or the like. The anti-oxidant may be incorporated with an ingredient of the composition made from the organic material followed by incorporation of the blend so prepared into the final composition. For example, in the case of a resin or ester gum plastic or liquid coating composition the anti-oxidant may be incorporated intimately with a plasticizer followed by intimate blending of the anti-oxidantplasticizer mix with the resin and other ingredients of the composition.

Incorporation may be effected by dissolving the anti-oxidant in a solvent therefor, which may be volatile or non-volatile, and which preferably is a solvent for or compatible with the organic material, and adding this solution to the organic material in any suitable manner. For example a solution of the anti-oxidant in paraihn oil may be added to rosin size during saponification of the rosin with the alkali. Such a solution may be milled or ground with the organic material or with the organic material and other components of the ultimate composition made therewith.

In the case of dry rosin size, the anti-oxidant may be incorporated with the size at any convenient time during the process for the production of-the size, or in fact, by addition to the size after it is produced. Generally speaking, however, the anti-oxidant will desirably and most effectively be incorporated with the size by adding the anti-oxidant or a solution thereof in paraffin oil to the autoclave in which the size is formed by saponiflcation of rosin, the addition being to the hot size during or after saponiflcation.

The anti-oxidant may be admixed with rosin by melting therewith. The intimate admixture of rosin and anti-oxidant may be cooled and granulated or powdered and sold as an article of manufacture for subsequent use in the forming of size, coating compositions, plastics, etc.

The amount of anti-oxidant incorporated with the organic material may vary within quite wide limits depending upon the nature of the organic material, the use to which it is to be put, etc. In general, the amount of anti-oxidant will not exceed a few percent by weight based on the weight'of the organic material and will usually be not over about 1% by weight of the organic material.

intimately incorporated,

Below are given several examples of embodiments of the present invention.

Emmple 1 One hundred sixty-eight g. aniline (1.8 mols) were treated with dry hydrochloric acid until the weight increased 10.2 g. (0.2 moi) of hydrochloric acid were thus added, forming 0.2 mol of aniline hydrochloride catalyst). 100 g. terpinyl betachloroethyl ether (0.48 mol) was mixture refluxed for 8 hours by heating in an oil bath at 200-210-C. The mixture was allowed to cool and was then agitated with 175 c. c. of 25% NaOH solution. The oil was separated, washed with NaCl solution and dried over solid NaOI-l'. The mixture was then distilled at reduced pressure. At 5 mm. pressure, excess aniline distilled over from 45 to 100 C. Thereafter cuts of condensate came over as follows:

Cut Pressure Yield addedandthe 10 Fell:

Each of the cuts was admixed with rosin i1 the same manner as in Example 1. Tests of th products for absorption of oxygen gave result comparable with mmple 1.

Example 3 Fifty g. of terpinyl beta-chloroethyl ether (0.2: mol) and 150 c. c. of a aqueous solution 0: trimethyl amine (0.76 moi) and about 0.1-0.2 g as catalyst were heated at C. for i hours in a sealed steel bomb. The reaction product consisted of two layers. The upper oil laye1 was soluble in dilute acid but insoluble in watei and in caustic. The oil layer was washed with of caustic and dried in a desiccator.

The resulting oily material was incorporated with I wood rosin by melting therewith in the amount of 1% by weight of the rosin, cooling and powdering. A sample was subjected to treatment with oxygen at room temperature and at 30 Lots of I wood rosin were mixed with 1% by weight on the weight of the rosin of each the above liquid products, cuts 1 to 3, by melting the rosin and the anti-oxidant together at 110 C., cooling and granulating. The mixtures were submitted to oxygen absorption tests at room temperature, the oxygen pressure being 30 lbs. per square inch. A blank of straight rosin containing no anti-oxidant was submitted to a parallel test. The results were as follows:

The figures in the last four columns indicate the percent increase by weight of the rosin-antioxidant mixture or of the blank. It will be seen that the antioxidant markedly reduces the oxygen absorption upon the passage of time.

Example 2 Eight hundred forty g. aniline was treated with dry H01 until the weight increased 36 g. (crystalline aniline hydrochloride separated out) 500 g. terpinyl beta-chloroethyl ether was added and the mixture refluxed for 8 hours in an oil bath at 190-i95 C. The mixture was then washed with 875 c. c. of 25% aqueous NAOH solution and then with water. The addition of NaCl to the washing water was necessary in order to break or prevent the formation of emulsions of the oily condensation product. The excess aniline was removed by vacuum distillation. Further distillation gave the following cuts of condensate in the form of viscous oils:

Cut 2223? Pressure Yield Example 4 Fifty g. of terpinyl beta-chloroethyl ether (0.23 mol) 12 g. ethylene diamine (0.21 mol) and 0.1 s. FeIz as catalyst were heated at 160-165 C. in a sealed vessel for 8 hours. The reaction product was a viscous red liquid together with considerable solids. The mixture was extracted with 206 c. o. of ether and insoluble solids filtered caustic and the solvent evaporated. The product was blended with rosin in the same manner as before and a lot thereof was subjected to oxygen at room temperature at 30 lbs. per square inch. The results are indicated in the following table:

Time in hours One hundred eight g. (0.5 mol) of terpinyl beta-chloroethyl ether, 186 g. aniline (2 mols), and 12.9 g. (0.1 mol) oi aniline hydrochloride were refluxed together for 8 hours. The reaction mixture was neutralized by treatment with 150 g. of 25% aqueous NaOH solution and the oily layer was dried over solid NaOH. Excess aniline was removed by distilling at 7 mm. pressure, the aniline passing over at a vapor temperature of -70" C. when the vapor temperature started rising rapidly to 0., all of the aniline had been removed and distillation was stopped. The residue consisted of g. or a dark-colored viscous liquid.

This liquid was incorporated as before with rosin in the amount of 1% by weight of the resin and a sample of the blend was subjected to oxygen at room temperature and at 30 lbs. per square inch. The results are indicated in the following table:

Increase in Time in hours weight Per CF!!! Example 6 The following mixture was milled 0n the usual two-roll rubber mill in the usual manner:

7 Grams Rubber 500 Reogen 5 Zinc oxide 25 Stearic acid 5 Captax 5 Condensate-Cut 2 of Example 1 5 Sulfur The condensate prepared as described in Example 5 was incorporated in the following manner into dry rosin size as an antioxidant therefor. An ethyl alcohol solution of about 0.5% by weight of the condensate based on the weight of rosin to be incorporated in the size, was added to a mixture of rosin, water and sodium hydroxide undergoing heating to effect saponification in an autoclave, the rosin and sodium hydroxide being used in proportions to produce a size containing about 5.0% free rosin. Thereafter saponification of the rosin was completed by continued heating and the saponified rosin mixture was spray dried in the well known manner into a relatively dry atmosphere for desiccation. The resulting dry size contained the condensate in uniform distribution, and exhibited excellent resistance to oxidation or spontaneous combustion.

Example 8 The condensate prepared by the method of Example 5 was incorporated in dry rosin size as follows: 0.5% of the condensate was dissolved in 3.0% of paraffin oil, both percentages being based on the weight of rosin employed in formulating the size. The rosin, solid NaOH, and distilled water employed in the usual proportions utilized in making dry rosin size, were cooked in an autoclave for 10 minutes whereupon the solution of antioxidant in the parafiin oil previously heated to a temperature of 120 C. was injected into the size cook which was at a temperature of about 120 C. The injection was followed by 10 minutes additional cooking whereupon the size was spray dried in the conventional manner.

From the foregoing, it will be seen that the present invention enables the preparation of compositions of improved properties particularly as regards resistance to oxidation and spontaneous deterioration or combustion. It will be seen that he invention is particularly applicable to the prevention of oxidation of rosin and dry rosin size where difficulties with oxygen deterioration have been a particularly great problem heretoore.

It will be understood that the details and examples hereinbefore set forth are illustrative only and that the invention as broadly described and claimed is in no way limited thereby.

As used herein, the term terpene radical" is intended to designate terpene hydrocarbon radicals, or substituted terpene hydrocarbon radicals, for example substituted with oxygen groupings, hydroxy groupings, ester groupings, aldehyde groupings, amino groups, halogen groups, sulphur groups, etc.

What I claim and desire to protect by Letters Patent is:

1. A composition of matter comprising an organic material which is normally subject to deterioration upon ageing in contact with oxygen and which is selected from the group consisting of rosin and rosin derivatives and an anti-oxidant therefor comprising a condensation product of an ether of the general formula T-O-RX, wherein T represents a terpent radical, R represents an aliphatic hydrocarbon radical, and X represents a halogen atom, with an amine.

2. A composition of matter comprising an organic material which is normally subject to deterioration upon ageing in contact with oxygen and which is selected from the group consisting of rosin and rosin derivatives and an anti-oxidant therefor comprising a secondary amine condensation product of an ether of the general formula T-O-RX, wherein T represents a terpene radical, R represents an aliphatic hydrocarbon radical, and X represents a halogen atom, with a primary amine.

3. A composition of matter comprising an organic material which is normally subject to deterioration upon ageing in contact with oxygen and which is selected from the group consisting of rosin and rosin derivatives and an anti-oxidant therefor comprising a tertiary amine condensation product of an ether of the general formula T-O-RX, wherein T represents a terpene radical, R represents an aliphatic hydrocarbon radical, and X represents a halogen atom, with a secondary amine.

4. A composition of matter comprising rosin and an anti-oxidant therefor comprising a con- The resulting dry size displayed good resistance to oxidation.

densation product of an ether of the general formula T-O-RX, wherein T represents a terpene radical, R represents an aliphatic hydrocarbon radical, and X represents a halogen atom, with an amine.

5. Dry rosin size resistant to oxidation comprising saponified abietic acid and an anti-oxidant therefor comprising a condensation product of an ether of the general formula T-O-RX, wherein T represents a terpene radical, R represents an aliphatic hydrocarbon radical, and X represents a halogen atom, with an amine,

6. A composition of matter comprising rosin and an anti-oxidant therefor comprising a condensation product of terpinyl beta-chloroethyl ether with an amine.

7. Dry rosin size resistant to oxidation and comprising saponiiied abietic acid and an antioxidant therefor comprising a condensation product of terpinyl beta-chioroethyi ether with an amine.

8. A composition of matter comprising rosin and an anti-oxidant therefor comprising a condensation product oi terpinyl bete-chioroethyi ether with a primary aromatic amine.

9. Dry rosin size resistant to oxidation and comprising saponifled abietic acid and an antioxidant th'erefor comprising a condensation 

